TWI303260B - Flameproof polyamide moulding compositions - Google Patents

Abstract

The invention relates to flameproof polyamide molding compositions, comprising 30-80% by weight of a semi-aromatic, partially crystalline polyamide and 1-30% by weight of a flame retardant containing a phosphinic acid salt and/or a diphosphinic acid salt.

Description

1303260 发明, the invention description: [Technical field of the invention] The present invention relates to a halogen-free flame retardant polyamine which is based on a semi-aromatic furnace and a partially crystalline polyamine, which is contained as a retarding combustion agent. The phosphonates are stable in their volume at high temperatures, and because of their advantageous combustion, these cast compounds are suitable for the manufacture of thin-walled articles, such as connectors, especially in the electrical and electronics industries. 'Dissolved dots are semi-aromatic hydrocarbons of 28G ° C. Partially crystallized poly- is widely used in the production of foundry composites, which enables production, for example, in the electrical and electronic industries, to have excellent volume stability at high temperatures. And it is possible to read articles that are very good in delaying the burning properties. Casting compounds of this type, for example, are required in the electronics industry for production in accordance with the so-called surface mount technology (SMT) inlays: on the board. In the application, these components must withstand a temperature of 27 °C in a short time (four), so that no change in volume occurs. Since very thin-walled components are produced especially in the electronics industry, it is necessary to classify the flammability in the casting compound used in this application according to UL94. [Prior Art] - prefers an elemental compound or red phosphorus as a retarding combustion agent for the production of a semi-aromatic hydrocarbon, a partially crystalline polyamine, which is higher than. The hot money of c, as in the production and processing of __ composites case EP〇41〇 and EP () 288 is known to use brookized polyphenylene as a flame retardant, from the European patent case EP 0 299 444 Know the use of red scales as a disk flame retardant. The anti-combustion polyamine containing (4) is not toxic in addition to other shortcomings because it has a substance in the incineration treatment. * There is a turn of the _ there are - the color of the time, the color change of the color < can be mixed. Furthermore, the production and processing of (4) semi-aromatics for retarding ignition 1303260 in the process of polyamines requires considerable safety and care, because high temperatures are required and toxic phosphine is formed. For these reasons, it is recommended to delay the combustion agent without the above-mentioned disadvantages. Thus, calcium and aluminum salts of phosphonic acid and bisphosphonate are used as retarding combustion agents for polyamines as described in European Patent No. EP 0 792 912. Polyamide 6 and polyamine 66 have been mentioned as being particularly suitable as polyamines. The cast composite thus obtained was classified according to UL94 to a flammability classification v〇 of a test piece having a thickness of 1.2 mm. While it is indicated that the phosphonates are suitable as retarding combustion agents in semi-aromatic polyamines, especially the possibility of incorporation into this type of polyamine at temperatures well above 300 °C is not provided. German Patent No. DE_A1 - 24 47 727 describes the use of phosphonates as retarding combustion additives for semi-aromatic polyamines. The semi-aromatic polyamines are softer in the softening range of less than 300 with respect to the amorphous polyamine. (In the following, the stability of its volume at high temperatures does not meet the requirements such as being embedded in components as surface mount technology. In US Patent No. 6,270,560, it is especially useful to combine aluminum phosphonates: Aluminum is used as a retarding combustion agent in polyesters and polyamides. This cited test proves its utility in polyesters, but does not indicate that it delays the use of combustion agents.

It is described in the patent WO 99/02606 that a condensation product of a metal salt of a phosphonic acid with melamine is used as a flame retardant for polyamidoamine, which also includes a semiaromatic hydrocarbon polyamine. According to this document, a semi-aromatic hydrocarbon, i.e., a high-melting point polyamine, has a weight percent of ruthenium metal as a retarding combustion agent to achieve a V0 classification according to UL94. High levels of this type of additive have a negative effect on the properties of the cast article. The example is shown in the glass fiber reinforced poly_A 6 6/6 T/6 I, combined with zinc phosphonate and melamine, reaching 16 coffee v flammable US patent US 2 rush _ 7888 A1 Aromatic Tobacco Poly 1303260 or Polyamide can be used to use non-i-organic organic delaying agents, phosphonic acid, ... strontium salts. The example shows the phosphonic acid in polyamine 6 combined with the use of red ^ ' ' ' in the test of UL94 measured 1 / 1V (about I · 6 mm) V0 flammability score * staff but not lion The contact acid salt is used as a retarding combustion agent in the high-viscosity semi-aromatic hydrocarbon polyamine. ^ For the melamine amine W compound described in the latest technical concept and equipped with the continuation of the kinetics, the VG flammability classification system is not less than 2 mm. Therefore, the V0 flammability classification condition of 0.4 bribes, such as those set by the electrical and electronic industries for the production of thin-walled castings, has not been met. SUMMARY OF THE INVENTION The present invention is directed to the present invention. The object of the present invention is to provide a polyamine-producing compound which inhibits bismuth, which contains a halogen-free delayed burning agent, and which satisfies the thickness of 0.4 leg test piece, V0 flammable. Conditions for sexual classification. # The present invention has been completed by the feature description of the scope of the patent application. The scope of the patent application is dependent on the specific embodiments of the invention. Eight surprisingly, it has been found that the use of phosphonates in semi-aromatic hydrocarbons, and at least 28 (). (: The Polylin towel is corrected to delay the burning to provide a thermoplastic conversion composite, its _« UL_94 _ (insurance test room) in 〇 · 4 _ test; t thickness VG flammability classification, the county is suitable for Production of very thin-walled <casting articles, especially for the production of electrical and electrical industrial devices without dentate j. Very good flame resistance. These cast articles have excellent high temperature tolerance (according to ISO 75 measured HDT/A), which can be used without limitation on surface-envelope. It also satisfies the increased conditions, which are transferred to the lead material of the lead. The processing temperature contributes to the technique. Therefore, the present invention is directed to a cast composite of a flame retardant polyamine which comprises ', 1303260 a) 30 to 80% by weight of a semi-aromatic hydrocarbon, a partially crystalline polyamine b) 1 to 30% by weight of a delayed combustion agent comprising a grade salt of the formula (I) and/or a dibasic salt of the formula (Π) and/or a polymer thereof

π ii ii if 〇 一卜 R3—Ρ—〇 (1) Μ

U (2) mm where R1 and R2 are the same or different and represent a linear or sub-type alkyl and/or aromatic hydrocarbon group having a carbon number of 1 to 6, and R3 represents a carbon number of 1 to 1 Å. a linear or bifurcated alkyl group, an aromatic hydrocarbon group having a carbon number of 6 to 10, an alkyl aromatic hydrocarbon group or an aromatic alkylene group; Μ representing the second or third major or minor group of the periodic table Metal ion; m represents 2 or 3; η represents 1 or 3; X represents 1 or 2, c) 5 to 60% by weight of fiber or particulate filler or a mixture thereof d) 0.05 to 10% by weight of additive The sum of a) to d) is ι〇0 by weight. The scorpion ice & amperage or molecular polymer can be used according to the invention as a semi-aromatic hydrocarbon, a partially crystalline polyamine, the units of which are derived from di-acids and: 1303260 amines, and also derived from amino groups Carboxylic acids or individual corresponding indoleamines. One of the suitable base acids is an aromatic hydrocarbon and a fatty acid of a dibasic acid such as terephthalic acid, m-benzene = formic acid, adipic acid, sebacic acid, sebacic acid, dodecane dicarboxylic acid, and clothing. Alkanedicarboxylic acid. Diamines suitable for diamines having a cyclic aliphatic chain, such as decanediamines, cyclodecanediamines, cyclodecanediamines, cyclododecanediamines, methylcyclopentanyl Diamines, i 4_cyclohexene diamines, dipyridylamino rings, hexyl methane, and mono-(3-methylaminocyclohexaneyl) methane. The suitable aminocarboxylic acids are amino red acid and aminododecanoic acid, which can also be used in the corresponding internal age, open / caprolactam or caprolactam (laur〇lactam) . The semi-aromatic polyamines have a melting point between 280 ° C and 340 ° C and are preferred between 295 ° C and 325 ° C. “Special Vatican preference is polyamine, which consists of terephthalic acid (TPS), isophthalic acid (IV)) and 7T methyldiamine, or terephthalic acid, adipic acid and hepta

, the composition of amines. The more favorable ratio here is approximately 70: 30 TPS: IPS, 疋55 · 45 TPS: adipic acid. In particular, the two special polyamines produce superior properties. According to Shuming's retarding combustion agent relationship, the salts of the salts of the general formula (I) and the phosphonates and/or the polymers thereof. Phosphonic acids suitable for the production of acid salts according to the invention are, for example, dimethylphosphonic acid, ethylmethylphosphonic acid, diethyl citric acid, fluorenyl-n-propylphosphonic acid, methyl carbaryl Methyl-phosphonic acid), ethidium 4,24 methylphosphine^), m (methylphosphonic acid), benzene-1,4-bis(decylphosphonic acid), nonylphenylphosphine ruthenium, diphenyl Phosphonic acid. The salt of the sand according to the present invention can be produced according to a conventional method as described in the example of European Patent No. 699 708. The linonic acid thus forms a polymer phosphonate with a metal nucleus, a metal hydroxide or a metal oxide, a substantially important monomer, in the case of an aqueous solution, depending on the reaction conditions. 1303260 The phosphonates of the formulae (1) and (9) may contain the second or third major metal ion of the surface, and the preferred ones are the amount of phosphonic acid and the salt. The material of the composition is called for use. The preference is to use powder to force application. The purpose is to achieve good dispersion in the embedding of the polymer towel. The casting compound according to the invention contains as a component b) having a weight ratio of 1 to 30, more preferably 8 to 2 G. a sulphate of the formula (1) and or a bisphosphonate of the formula 11 and/or a polymer thereof. According to the material of (4), the compound contains $ to (9) weight = light lix charge _ or its age. Field Green Filler ... An example of tincture can be mentioned, such as glass fiber, carbon fiber, you know, vitamin potassium whisker, preferred glass fiber. · ^Man casting cohabitation Glass fiber can be carried out in the form of a jointless fiber (roving) or in the form of a cut-shaped 3 fiber. In order to improve the compatibility with the semi-aromatic polyamide, it is treated with a veneer or an adhesion promoter. The diameter of the commonly used glass fiber ranges from 6 to 20^1111. In particular, glass balls, lime, powdered quartz, talc, turnstone, kaolin, and 2 mothers all cooperate to form a particulate fiber. A. As an additive of the component d), for example, there are a thermal stabilizer, an antioxidant, a uv retanning agent, a processing agent, a releasing agent, a nucleating agent, a dyeing agent, and an anti-drip agent. The fire-resistant poly-complex according to the present invention can be produced in accordance with a conventional method. To this end, the ingredients are pre-mixed and then f-formed in a remedy. f see the process of pure content through the individual = pre-component a) to d) in a sequential (four) way or already mixed well plus < compound machine. The homogenization of the polymer melt is determined by the secret of the semi-aromatic polyamine in 29 (rc to 3 thieves). The common melt 1303260 is wiped out with a thread and then Cooling and granules. The conversion composite according to the present invention is suitable for use in the production of cast articles according to the injection conversion method. The present invention further relates to the use of the above-described casting compound & In the case of the invention of composites, special emphasis should be placed on the conditions suitable for the production of cast articles that meet the UL94s〇4mm test piece thickness flammability classification V0. It cannot be known in advance by the latest technical standards, as in the next It is also shown herein that it can be supported by comparative examples, that is, polyamines not belonging to the selected category of the invention cannot meet this requirement. If the foundry compound is used, for example, in the electrical industry as production according to the so-called surface mount technology SMT, Such cast compositions are particularly preferred when they are embedded in components on a printed circuit board. In this application, the components must actually be short-lived. The inter-stand temperature is 270 ° C without change in volume. The components that meet this condition should therefore be classified according to the V0 flammability according to UL 94 at 0.4 mm. The following examples use the following ingredients: a) Polyamine 1 polyamine 6 butyl / 66 has a molar ratio of terephthalic acid to adipic acid of 55: 45 Polyamide 2 polyamine 6T / 6I with terephthalic acid and m-benzene The molar ratio of dicarboxylic acid is 70 ·· 30 polyamine 3 polyamine 66 (comparative group) component b) aluminum dimethylphosphonate (made from dimethylphosphonic acid and aluminum hydroxide) Calcium ethylphosphonate (prepared from methyl ethylphosphonic acid and cerium oxide) 1303260 Ingredient C) Standard porphyrin for polyamidamine, fiber length 45 mm, diameter 10 μηι 〇 component d)

Irganox 1098 (Ciba special product) Calcium stearate [Embodiment] Examples The ingredients are listed in Table 1, and are expressed in weight percent by a ZSK3 crucible twin-screw extruder manufactured by Werner & pfleiderer. Composite into a casting ^ product. Ingredients a) and d) are premixed, and then component b) is applied via a suitable vest 5 to the can feed zone. The supply of the face fibers is carried out via a secondary feeder. The homogenization of these components is carried out at a temperature of 3〇〇i 3 . The cast composites are extruded in the form of strands, which are then granulated. The granules are dried to the present; / ^ ^ is processed into a test piece on an injection casting machine. Followed by • According to UL-94 for thickness 〇.4 mm!|Words, y, flammability test, general conditionalization • Tensile E-modulus test according to ISO 527, 浐• according to Brain 17 coffee under the hunger for impact H casting ^, according to IS0 75 for thermal deviation temperature test, HDn | coal as cast ^ 12 1303260 Table 1

Comparative Example Example 1 Example 2 Weight percent composition Polyamide 1 55.4 Polyamide 2 46.4 Polyamide 3 55.4 Aluminum dimethylphosphonate 14 14 Calcium methyl ethyl laurate 18 Glass fiber 30 30 35 Irganox 1098 0.25 0.25 0.25 Calcium stearate 0.35 0.35 0.35 Test UL-94 flammability test classification 0.4 mm V-0 V-0 0.8 mm Vl V-0 V-0 1·6 mm V-0 Tension E-modulus 10400 12200 14000 HDT/A Mpa 248 287 285 °C

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Claims (1)

1303260 Pickup, Patent Application Scope · A cast composite of flame retardant polyamide, which consists of: a) 30 to 80 weight percent of a semi-aromatic hydrocarbon, partially crystalline polyamine; b) 1 to 30 weight percent a retarding combustion agent comprising a phosphonate of the formula (I) and/or a bismuth citrate of the formula (Π) and/or a polymer thereof OUP A 1 ΟΛ R ^ Γη Μ Ο Q "r' R2 R3 1OI^IR ο Μ π wherein R and R are the same or different and represent a linear or branched alkyl group and/or an aromatic hydrocarbon group having a carbon number of 1 to 6; R3 represents a carbon number of 1 to a linear or bifurcated base of 10, an aromatic hydrocarbon group having a carbon number of 6 to 10, an alkyl aromatic hydrocarbon group or an aromatic alkylene group; M represents the second or third major or minor periodic table Group of metals is given; m stands for 2 or 3; Π stands for 1 or 3; Χ stands for 1 or 2, c) 5 soil 60% by weight of fiber or particulate filler or a mixture thereof 14 l3〇326〇__________ q Moon Sleeve (more) jade replacement page 1111 ^ d) 0. 05 to 10% by weight of additives selected from stabilizers, processing aids, anti-drip agents a dyeing agent and/or a pigment; a total of 1% by weight of the total of a) to d). The casting compound of the flame retardant polyamide according to claim 1 of the patent application, characterized in that the semi-aromatic The hydrocarbon polyamine has a concentration of at least 280 ° C. The casting compound of the fire-resistant polyamide according to claim 1 is characterized in that the semi-aromatic polyamine a) is selected from Such a group of polyamine formations, the unit of which is repeated from terephthalic acid. 4. The casting compound of the flame-retardant polyamide according to claim 3 of the patent application, characterized in that the half The aromatic hydrocarbon polyamine a) is selected from the group consisting of such polyamines to form ruthenium. The unit of the repeat is derived from terephthalic acid and adipic acid. 5. The flame retardant according to claim 3 A polyamine casting compound characterized in that the polyamine is formed from terephthalic acid (TPS), isophthalic acid (IPS), and cyclohexane diamine. The casting compound of the anti-flammable polyamine described in the above 5 is characterized in that the polyamine contains TPS and IPS The example is about 7: 30 〇7· The cast composite of the flame-retardant polyamide according to the fourth aspect of the patent application, characterized in that the polyamine is composed of terephthalic acid (TPS) and An acid and a cyclohexanediamine are formed. 8. The cast composite of the flame retardant polyamide according to claim 7 of the patent application, characterized in that the polyamine contains a ratio of TPS to adipic acid. Approximately 55:45. 9. The cast composite of the fire-retardant polyamide according to claim 1 of the patent application, characterized in that it is used as a retarding combustion agent b), the user of formula (1) Salts and/or salts of bisphosphonates of the general formula (II) and/or their polymers, Μ 15 1303260 竹年七修 (吏〗 is replaced by page 丨 indicates #5 or Ming ion. 10. A cast composite of a flame retardant polyamide according to claim 1 of the patent application, which is applicable to the production of cast articles. 11. The cast composite of the flame retardant polyamide according to claim 10, which is used for producing a cast article satisfying the condition of the flammability class V0 found in a test piece having a thickness of 0.4 mm according to UL94. 16